Coating and curing apparatus and methods

ABSTRACT

Disclosed are coating apparatus including flow coating and roll-coating that may be used for uniform sol-gel coating of substrates such as glass, solar panels, windows or part of an electronic display. Also disclosed are methods for substrate preparation, flow coating and roll coating. Lastly systems and methods for skin curing sol-gel coatings deposited onto the surface of glass substrates using a high temperature air-knife are disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of the following U.S. patentapplications, each of which is incorporated by reference in itsentirety: U.S. application Ser. No. 13/835,253, filed Mar. 15, 2013(ENKI-0003-U01), which claims priority to U.S. Application No.61/762,603, filed Feb. 8, 2013 (ENKI-0003-P01).

BACKGROUND

1. Field

The present disclosure relates generally to the field of thin-filmsol-gel coatings and in particular to coating on substrates such asglass or solar panels.

2. Description of the Related Art

Thin-film sol-gel coating refers to a technique of coating substrates,such as optical surfaces, windows, solar panel surfaces, and the like,using a wet chemical formulation called a ‘sol’ that undergoes a‘gelation’ process wherein it polymerizes to form a solid thin-film on asubstrate. These thin-films often undergo a subsequent curing step toincrease mechanical strength and other properties. This curing is oftenaccomplished by heating or irradiating the substrate and coating.Thin-film sol-gel coating is a very versatile process that has manyindustrial uses such as formation of dielectric layers on semiconductorwafers and water repellent layers on ceramics. There are several welldocumented techniques for applying wet sol to substrates, some of whichare in widespread industry use and others that have generally beenlimited to the laboratory. Industrial scale sol-gel coating is mostcommonly performed by a dip, spray, aerosol deposition, spin, meniscus,slot-die or roller process. There are also several methods used to curesol-gel thin films including baking in ovens, treatment with microwave,infra-red or ultra-violet radiant energy, and exposure to flowing hotgases. These methods may or may not work in concert with components ofthe coating that catalyze or otherwise aid the curing process.

In the dip coating process the substrate to be coated is dipped into atank containing the sol. It is then withdrawn at a process dependentspeed. As the substrate is slowly drawn from the sol, the gelationprocess occurs just above the surface and a thin-film layer forms. Dipcoating processes are inherently two sided in that all sides and edgesof the substrate are coated. This can be advantageous if complete solcoverage is desired but is disadvantageous if the coating on someportion of the substrate interferes with a later substrate processingstep. The dip coating technique requires a tank slightly larger than thesubstrate, which for large substrates means the tank may hold a largevolume of sol. For sols mainly composed of organic solvents this maypose a vapor and flammability hazard. It may also be challenging tocontrol the composition and quality of the sol within the large tank.Each new substrate dipped in the tank may carry contamination that istransferred to the sol; the sol might become depleted in some element asmore substrates are processed causing a variation in the thin-filmproduced. The sol may change through evaporation of solvent at thesurface where substrates are introduced.

Spray coating exists in many forms, but generally may be considered tobe the deposition of material through a nozzle under pressure or theatomization of material which is then entrained by a jet of gas. In allcases the material is moved across a gap between a nozzle and a surfaceto be coated. The purpose of the spray system is to deposit a uniformlayer of material over a wide area of the substrate. In the context ofsol-gel coatings on substrates spray coating has the advantage of onlyapplying fresh material to the substrate. Careful selection of solventsand control of solvent evaporation is needed to ensure that the correctfinal concentration of sol is delivered to the substrate. Sprayingtypically requires that either the nozzle or the substrate is moved inorder to coat an area, for example the substrate may be moved past aline of stationary nozzles.

Spin coating is commonly used in the semiconductor wafer processingindustry and in the LCD display panel industry to apply even layers ofmaterial to the surface of flat substrates such as silicon wafers orlarge pieces of glass. It has the same advantage as spray coating inthat only fresh material is deposited. It also has excellent uniformitycontrol. Generally, equipment to perform the spin coating tends to becomplex and costly to maintain because of the fine mechanical controlneeded to achieve uniformity. This is particularly true as the size ofthe substrate increases.

Meniscus coating was historically used in the semiconductor industrybefore giving way to spin coating. It remains in use by some equipmentvendors in the LCD display industry. Meniscus coating works by passing asubstrate to be coated over a narrow slot at a very close distance suchthat material forced up through the slot forms a continuous meniscuswith the substrate. As the substrate moves across the slot this meniscusdeposits a layer of material on the substrate. The technique requiresfine control over the distance between the slot and the substrate acrossthe full length of the slot. Generally, the substrate must be extremelyflat to avoid deviation in this distance. Additionally, this techniqueworks best with viscous materials that can form a large meniscus. Thislimits its usability with sol-gel formulations that use comparativelylow viscosity solvents.

Roll coating is a common application method for sol-gel coatings on flatsubstrates. In one embodiment of this process, material is depositedfrom a reservoir onto an application roller. A doctor blade or doctorroller may be used to control the thickness of the coating materialplaced on the application roller. That material is then transferreddirectly from the application roller to the substrate. In general, rollcoating works best with continuous substrates, such as, for example, aroll of steel. In the case of discontinuous substrates such as pieces ofglass or wood, for example, special techniques may be employed tocontrol coating uniformity at the leading and trailing edges of thesubstrate. These techniques include, for example, varying theapplication roller contact pressure by having the coating rollertouch-down on the leading edge and lift-off the trailing edge in aprecisely controlled manner. The application roller may run in a forwarddirection, i.e. rolling with the substrate direction of movement or in areverse direction, wherein the application roller opposes the directionof movement of the substrate. The surface of the application roller maybe made of a compliant material that serves to compensate for anysurface or flatness variations on the substrate and to provide a surfaceto which the coating material will adhere in a reasonably uniformmanner, or the application roller may be a comparatively solid material.Depending on the rheology of the material to be coated, the surfaces ofthe rollers may be patterned with grooves or other textures to add incoating application.

Flow coating is a technique where coating material is flowed over asurface to be coated. The excess drips away and that which remains onthe surface forms the final coating. The surface may be flat orirregular. In general, the substrate is oriented such that the coatingmaterial flows due to gravity. Advantages of this technique are itssimplicity, ability to coat irregular surfaces, and the option to useonly fresh material or to recirculate the excess material that drips offthe surface.

It would also be preferable to enable drying and curing of such coatingsat relatively low temperatures, such as below 150° C. so that thecoatings could be applied and dried and cured on substrates to whichother temperature sensitive materials had been previously attached, forexample a fully assembled solar panel.

The curing process for sol-gel films is a separate process that occursafter the gelation of the sol-gel material. One common cure method is toheat a sol-gel coated article in an oven. This has the advantage ofsimplicity. The oven may be of the batch type wherein a batch of coatedmaterial is placed in an oven that is then sealed, and maintained for aperiod, then opened and the batch removed. While in the oven, the coatermaterial may be subject to a varying temperature profile created by theoven's controller. Alternatively, the oven may be of the continuous typewherein a conveyor belt or similar transport mechanism moves coatedarticles through a heated container. As the material moves through thecontainer it may experience different temperatures in different zonescreating a temperature profile consisting of heating, soaking at a fixedtemperature, then cooling. The profile may be a function of thetemperature zones within the oven and the speed of the transportmechanism. Heat within the oven may be provided by convection with hotgases created by combustion of fuel gas or by the heating of gas byelectrical elements. Alternatively, the coated article might be heatedby radiant heat.

Some types of sol-gel coatings may be cured with ultra-violet radiation.In these types of materials, chemical crosslinking within the materialis promoted by high-energy photons.

For the curing of thin coatings on surfaces, hot gasses may be passeddirectly over the thin-film to heat the surface layer by conduction.

Optimal methods for industrial scale sol-gel coating of flat substratesshould be capable of selectively coating just one face of a substrate;be economical in their use of the coating material; provide easycompositional and contamination control; be versatile with respect tothe sol-gel formulation such that solvents of different volatilities canbe used and chemically compatible with critical equipment; be of lowcomplexity and cost; capable of handling large imperfections insubstrate surface flatness, and capable of achieving superior coatinguniformity. Optimal curing methods should be cost effective; not damagethe coated substrate; match the through-put of the prior coating processstep and effectively cure the coating material to its final desiredproperties.

SUMMARY

In an aspect, a coating and curing apparatus may include a conveyorsystem of a combination roll coating and curing facility, wherein thecombination roll coating and curing facility comprises at least one rollcoating facility and at least one curing facility, and wherein theconveyor system is adapted to transport a substantially flat substratethrough the combination roll coating and curing facility, a processorthat controls a process parameter of the at least one roll coatingfacility, and an air knife of the at least one curing facility, whereinthe air knife is adapted to direct heated air to a portion of the flatsubstrate as it is transported through the at least one curing facility,wherein the at least one roll coating facility is adapted to coat thesubstantially flat substrate with a sol gel coating material. Thesubstantially flat substrate may be a part of at least a partiallyfinished solar module. The apparatus may further include an electricalelement disposed within the air stream to heat the air flowing throughthe air knife. The air may be heated to a temperature between about 300°C. and 1000° C. The apparatus may further include a fan in the airstream that directs air to the air-knife. The apparatus may furtherinclude an electronic controller that controls the temperature based onreadings from at least one temperature sensor located in the air stream.The apparatus may further include an exhaust to remove heated air fromthe apparatus. The apparatus may further include a flat plate attachedto the leading edge of the air-knife, wherein the flat plate is adaptedto form a pre-heat chamber with the top surface of the substantiallyflat substrate. The apparatus may further include an infra-red emitterdisposed along the conveyor system prior to the air knife, wherein theinfra-red emitter is adapted to heat the substantially flat substrate toa temperature of between 25° C. to 200° C. The apparatus may furtherinclude an infra-red emitter disposed along the conveyor systemsubsequent to the air knife, wherein the infra-red emitter is adapted tomaintain the flat substrate at a temperature of between 120° C. to 400°C. The process parameters may include at least one of a doctor rollerspacing and/or pressure to an application roller, the application rollerspacing or pressure taken with respect to the substantially flatsubstrate, a speed at which the substantially flat substrate is conveyedby the conveyor system, and in the case of reverse roll-coating, adifference in speed between the substantially flat substrate and theapplication surface of the application roller. The processor may furthercontrol a process parameter of the curing facility. A plurality of rollcoating facilities and curing facilities may be arranged sequentially.The air-temperature exiting the air knife may be between 500° C. to 750°C. The speed of the substantially flat substrate on the conveyor systemmay be between 0.25 cm/s and 3.5 cm/s. The resulting temperature of asurface of the substantially flat substrate may be between 150° C. to600° C.

In an aspect, a method of coating and curing may include conveying asubstantially flat substrate to be coated with a conveyor system througha combination roll coating and curing facility, wherein the combinationroll coating and curing facility comprises at least one roll coatingfacility and at least one curing facility, roll coating thesubstantially flat substrate with a sol gel coating material with the atleast one roll coating facility, and curing the sol gel coating materialon the substantially flat substrate with an air knife of the at leastone curing facility, wherein the air knife is adapted to direct heatedair to a portion of the substantially flat substrate as it istransported through the curing facility by the conveyor system. Asol-gel coated substantially flat substrate may be formed by the method,wherein a portion of the sol-gel coating material is cured while adifferent portion of the sol-gel coating material remains uncured.

In an aspect, a method of tuning the performance of a sol gel coatingmay include determining a desired cure temperature profile to achieve aspecific performance metric for a sol gel coating using at least onephysical analysis method, selecting settings for an air knife curingsystem's operating parameters to achieve the desired temperatureprofiles for the sol gel coating on a substantially flat substrate, andcuring the sol-gel coating on the substantially flat substrate with theair knife curing system. The at least one physical analysis method mayinclude at least one of thermogravimetric analysis, Fourier transforminfrared spectroscopy, ellipsometry, nanoindentation, abrasion testing,spectrophotometry, and a water contact angle measurement. The air knifecuring system operating parameters may include at least one of substratespeed, air knife air-flow volume, air knife output air temperature, airknife opening distance to substrate surface, a temperature set-point fora pre-heating zone and a temperature set point for a post heating zone.The performance metric for the sol-gel coating may include at least oneof hardness, abrasion resistance, surface energy, refractive index,optical transmission, thickness and porosity. The method may furtherinclude a step of coating the substantially flat substrate with the solgel coating using a roll-coating system before the step of curing. Asol-gel coated substantially flat substrate may be formed by the method.The specific performance metric may include a hardness of the sol-gelcoating within a range of 0.2 GPa to 10 GPa. The specific performancemetric may include a test in which no more than 1% of absolute opticaltransmission is lost after at least 500 strokes of an abrasion testperformed in accordance with specification EN1096-2. The specificperformance metric may include a water contact angle where the watercontact angle is within 60° to 120°. The specific performance metric mayinclude a water contact angle where the water contact angle is within 5°to 30°. The specific performance metric may include a refractive indexof the cured, coated sol gel from 1.25 to 1.45. The thickness may beapproximately 50 nm to 150 nm. A sacrificial component of the sol-gelcoating may be volatilized to form a desired porosity.

These and other systems, methods, objects, features, and advantages ofthe present disclosure will be apparent to those skilled in the art fromthe following detailed description of the preferred embodiment and thedrawings.

All documents mentioned herein are hereby incorporated in their entiretyby reference. References to items in the singular should be understoodto include items in the plural, and vice versa, unless explicitly statedotherwise or clear from the text. Grammatical conjunctions are intendedto express any and all disjunctive and conjunctive combinations ofconjoined clauses, sentences, words, and the like, unless otherwisestated or clear from the context.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosure and the following detailed description of certainembodiments thereof may be understood by reference to the followingfigures:

FIG. 1 depicts an embodiment of flow coating;

FIG. 2 depicts a cross-sectional view of an embodiment of a flow coatinghead;

FIG. 3 depicts a cross-sectional view of a second embodiment of a flowcoating head;

FIG. 4 depicts an isometric view of a flow coating head lower slotmanifold;

FIG. 5 depicts a partial view of the assembled flow coating head of FIG.2 and a corresponding substrate;

FIG. 6 shows a schematic cross-sectional view of a coating slotidentifying several critical dimensions and parameters;

FIGS. 7 a and 7 b depict a roll-coat system optimized for coating onflat substrates;

FIG. 8 depicts an embodiment of a roll-coat system for flat substrates;

FIG. 9 depicts an embodiment of a skin-cure system;

FIG. 10 depicts an example temperature profile for a skin-cure system.

FIG. 11 depicts an example of thermogravimetric analysis ofrepresentative samples of coating material.

FIG. 12 a, FIG. 12 b and FIG. 12 c show data for an exemplary sol-gelcoating that demonstrate control of final film thickness, refractiveindex and water contact angle as a function of maximum cure temperature.

FIG. 13 depicts an example of FT-IR analysis of representative samplesof coating material before and after the curing process.

DETAILED DESCRIPTION

Various embodiments of the disclosure are described below in conjunctionwith the Figures; however, this description should not be viewed aslimiting the scope of the present disclosure. Rather, it should beconsidered as exemplary of various embodiments that fall within thescope of the present disclosure as defined by the claims. Further, itshould also be appreciated that references to “the disclosure” or “thepresent disclosure” should not be construed as meaning that thedescription is directed to only one embodiment or that every embodimentmust contain a given feature described in connection with a particularembodiment or described in connection with the use of such phrases. Infact, various embodiments with common and differing features aredescribed herein.

FIG. 1 depicts an embodiment of laboratory scale flow coating. Inembodiments, a nozzle (101) dispenses a material (102) onto an inclinedsubstrate (103) as it is moved across the top edge of the substrate. Thematerial flows down the substrate, and the excess drips from the bottomedge of the substrate. The material that remains adhered to thesubstrate undergoes a gelation process as it dries and forms a thin-filmcoating on the substrate.

While the basic laboratory system shown in FIG. 1 can be scaled up insubstrate size, its rate of coating may be slow and wasteful of coatingmaterial. It is possible to recover the coating material that drips offthe bottom edge and recycle it to the nozzle, but this makes control ofcomposition and contamination of the recycled material difficult. Whatis needed is a flow coating system that has a fast coating rate and thatis economical with coating material with minimal wastage dripping fromthe bottom edge, without recycling of this material.

In one embodiment, a coating head such as the one shown in FIG. 5 and incross-section in FIG. 2 may be used in flow coating. The coating headincludes a long slot (116) formed between a lower slot manifold (110)and an upper slot manifold (111). This slot is positioned parallel toand extends along the length of the top edge of an inclined substrate(120). In an embodiment, the slot is approximately as long as the edgeof the substrate to be coated. For example, the slot may be orientedalong the longer edge of a rectangular substrate, such that the fluidflows down the substrate along its shorter edge. This orientationminimizes the time required for gravity to carry the fluid across theentire area of the substrate. In an embodiment, a distribution blade(112) bridges the gap between the slot and the top edge of the substratesuch that coating material flowing out of the slot is deposited on tothe distribution blade and then flows under gravity to the bottom of thedistribution blade, which contacts the front surface of the substratejust below the top edge of the substrate. The coating material thenflows off the distribution blade onto the front surface of the substrateand from there down the substrate until eventually it either drips fromthe bottom edge or is removed by other means. The length of thedistribution blade is slightly longer than the length of the slot and ofthe edge of the substrate that is being coated. In an embodiment, thedistribution blade extends beyond each end of the slot manifoldassemblies. For example, the distribution blade may extend 2-100 mmbeyond each end of the slot manifold assemblies. In another example, thedistribution blade may extend 10 mm beyond the substrate.

Coating material is supplied to the slot by a dispensing system, such asa pump (not shown) capable of transferring the liquid coating material,and that is also capable of delivering a measured quantity of coatingmaterial through one or more inlet ports (113) in the lower slotmanifold. The inlet port directs material into a corresponding internalpocket (114) within the lower slot manifold that allows the coatingmaterial to accumulate below the lip of the slot and to spread evenlyalong the slot before it begins to overflow the slot and flow onto thedistribution blade, providing a uniform fluid front of material over theblade. FIG. 4 shows an isometric view of the internal detail of a lowerslot manifold (110). The coating material flows from the port inlet,located in the middle of the internal pocket, outwards toward the endsof the internal pocket and so is distributed evenly along the back sideof the slot lip (140). Once enough material has filled the internalpocket it will begin to overflow the slot lip evenly along the length ofthe slot. The upper slot manifold (not shown in FIG. 4) forms theopposing side of the slot. A seal channel (141) may allow the assemblyto close to the appropriate slot width, as is described herein.

Producing high quality coatings of uniform thickness onto the substratemay depend on the rate at which the fluid flows through the slot. Inturn, the rate at which the material flows may be highly dependent uponseveral factors of the design including the slot length (l), width (w)(152) and height (h) (151), as seen in FIG. 6, the viscosity (μ) anddensity (ρ) of the coating material, and the pressure differential (ΔP)over the width of the slot. In an embodiment, the fluid flow in the slotis both laminar and has a fully developed velocity profile upon exitonto the distribution blade. Laminar flow in the slot can be achieved byensuring the fluid has a Reynolds number less than 1,400. In anembodiment, the Reynolds number (R_(e)) of the coating fluid within theslot is less than 100. The coating fluid may exit the slot with avelocity profile that is independent of subtle edge effects, turbulenceand other disturbances present at the coating fluid's entry into theslot. This condition can be achieved by ensuring the width of the slotis significantly longer than the flow's characteristic entrance length(L_(e)). In an embodiment, the slot width is equal to at least 10 timesthe entrance length. Such a condition is governed in the followingrelation, which uses the Blasius approximation to solve for the entrancelength between parallel surfaces:

$L_{e} = \frac{{hRe}_{h}}{100}$

The volumetric rate at which the coating fluid flows through the slot isclosely approximated by the following relation:

$Q = \frac{l\; \Delta \; P\; h^{3}}{12\; w\; \mu}$

With average flow speed, V, determined by:

$V = \frac{Q}{lh}$

In an embodiment, sol coating flow rates per unit slot length of between5×10⁻⁹ and 5×10⁻⁴ m²/s are useful for coating glass substrates of highquality, and uniform thickness. In an embodiment with a 2 meter longslot, this equates to a volumetric flow rate between 1×10⁻⁷ and 1×10⁻³m³/s. To prevent splatter or turbulent flow or other undesirablephenomena from impacting the distribution blade or substrate, coatingmaterial may not be forced from the slot under high pressure or flowrates. For example, gravity force may be used to drive fluid from theinternal pocket to the distribution blade. In an embodiment, the slot isdesigned such that for the chosen coating material properties, the flowrate out of the slot is less than the flow rate into the internalpocket. This has the effect of building a reservoir of coating materialbehind the slot in the internal pocket, forcing it to spread evenlyunder the influence of gravity along the entire length of the slot andto build up a head height H (150), as in FIG. 6, inside the internalpocket. If the flow rate through the slot is too high, then coatingmaterial will completely flow through part of the slot before spreadingalong the entire length of the slot and reaching the ends furthest awayfrom the inlet port. If the flow rate is too low, then the internalpocket may completely fill with coating material causing an increase inpressure that will create uneven flow rates and excessive back pressureon the coating fluid, and adversely affect the flow rate through theslot. All of these issues can cause the slot flow rate to vary and canaffect the quality and uniformity of the coating. The pressure drop overthe slot width, ΔP, can be related the fluid head height within theinterior pocket, H (150), the internal pocket pressure P_(o) (154),pressure at the entrance to the narrow slot, P₁ (153), and the pressureat the exit of the slot, P₂ (155), the fluid material density ρ and thegravitational constant g according to the following relationship:

ΔP=P ₁ −P ₂

ΔP=ρgH+P _(o)

This pressure input as a function of head height, combined with thedesired flow rate drives the desired slot height, h (151). As a result,careful consideration should be paid to the pressure in the internalpocket. Some embodiments keep the internal pocket sealed via a gasket,o-ring or sealant such that pressure is controlled by the relative flowrates of coating material into and out of the pocket. Other embodimentsmay include vents between the internal pocket and ambient pressure or toan auxiliary pressurization system. In an embodiment, pressure insidethe pocket is vented to the atmosphere and slot height, h, is determinedby the following relationship:

$h = \sqrt[3]{\frac{12\; {Qw}\; \mu}{l\; \rho \; {gH}}}$

Given the above parameters, for a typical sol coating, the width of theslot is between 0.05 and 2 mm, and preferably 0.1 to 0.5 mm. This widthmay be controlled by placing shims between the upper and lower slotmanifolds. Alternative embodiments may use machined steps or other gapcontrol methods. The assembly of upper and lower slot manifolds may havea gasket-like seal along the top and sides to ensure material isdirected towards the slot. An O-ring or similar internal pocket seal mayallow the assembly to close to the appropriate slot width, and may befacilitated with the use of a seal channel (141).

The distribution blade may serve at least three functions in enablingconsistent and uniform coating thickness; 1) it provides a path forcoating material to flow from the slot to the substrate; 2) it has ahigh energy surface that causes the material to spread evenly by surfacetension during its travel from the slot to the substrate; and 3) itprovides an interface to the substrate surface that is tolerant ofimperfections in flatness or warping of the substrate. In oneembodiment, the distribution blade is relatively more flexible than thesubstrate and is able to conform to an uneven or warped substrate. Forexample, the distribution blade is 316L stainless steel, 2020 mm long,45 mm wide and 0.38 mm thick and the substrate is tempered soda-limeglass 1970 mm long, 984 mm wide and 3.2 mm thick. In another embodiment,the distribution blade is relatively more rigid than the substrate and amechanism clamps the substrate to the back surface such that it is heldflat against the distribution blade. In one embodiment, the distributionblade has a surface energy between 25 mN/m and 100 mN/m.

The coating material exiting the head slot may not naturally form acontinuous curtain or ‘waterfall’ of coating material in the absence ofthe distribution blade, and instead, the coating material may exit theslot with many drips or small rivulets of material all along the lengthof the slot which may not result in a consistent or uniform thicknesscoating on the substrate. To achieve a curtain or “waterfall” out of theslot head in the absence of the distribution blade would requiresignificantly greater flow rates of coating material, and couldtherefore result in significant waste of coating material. Thus, thedistribution blade enables a consistent and uniform thickness coatingwith minimal material waste.

In FIG. 2, the distribution blade is a thin piece of material that isheld in place by a backing plate (118) that along with the distributionblade is attached to the upper slot manifold (111) by a plurality ofbolts or other fastening means (119). This backing plate also serves totension the distribution blade by forcing it forward at a slight angle.This reduces warping of the thin distribution blade along its length.The upper and lower slot manifolds are held together by a plurality ofbolts or other fastening means (117). In some embodiments the bottomedge of the thin distribution blade may be beveled or rounded. In apreferred embodiment it is beveled between 15° and 60°.

In some embodiments the distribution blade is made from a stainlesssteel alloy such as 316L. In other embodiments it could be made fromtitanium, chrome or nickel plated steel, various corrosion resistantalloys, glass, ceramics, polymer or composite materials such as a metalcoated polymer. The material may be chosen to be chemically resistant tothe composition of the coating material such that it is not damaged bythe coating material and such that it does not contaminate the coatingmaterial in any way.

In FIG. 2, the lower slot manifold has a notch (115) just below theslot. The purpose of this notch is to prevent the flow of coatingmaterial from the slot along the bottom edge of the lower slot manifoldand from there dripping on to the distribution blade or the substrate.

FIG. 3 shows an alternative embodiment of a distribution blade (130)wherein the blade is a solid piece of material that also forms the upperslot manifold. The front surface of the blade (132) acts to distributethe coating material evenly from the slot to the substrate. The bottomedge of the blade is profiled (133) to facilitate the flow of coatingmaterial from the blade onto the substrate. It should be understood thatthe exact shape of this profile can include curved or angled flat bevelsand that the transition of angle from the face of the distribution bladecan range from gradual to abrupt and that the final angle that the edgemakes with the substrate surface can be from 10° (sharp) to 110° degrees(obtuse). In another embodiment, the thick or solid distribution bladedoes not also form the upper slot manifold, but is instead a separatepiece that is bolted onto the slot manifold in a manner similar to thethin distribution blade shown in FIG. 2.

Some embodiments of the distribution blade include coatings or surfacetreatments on the front side (that is the wet side) and on the backside. For example, a front side surface treatment may enhance thespreading of the coating material as it flows to the substrate. Aback-side treatment might repel the coating material to suppressmaterial gathering on the backside due to capillary action that thendripped onto the substrate as it was removed from the distribution orgather on the backside and contaminate the next substrate positionedagainst the blade. Other embodiments of the distribution blade includelaminates and composites where dissimilar materials are fused orassembled together to provide differences between the front and backsidesurface properties as might also be achieved in the case of a coatedmetal blade.

Some embodiments of the coating head manifolds may have coatings orsurface treatments to protect them from adverse chemical reactions withthe coating material or to change how the coating material flows withinthe internal pocket or over the slot lip.

A full coating head may be composed of a plurality of slot manifoldassemblies. For example each slot manifold assembly might be 50 cm long.Four such assemblies may be mounted on a supporting structure such thatthey form a 200 cm long coating head. The dimensions of the slotmanifold assembly and the number of such assemblies used for aparticular length of coating head may be selected to manage the cost ofmanufacturing the slot manifolds themselves and the complexity ofconstructing the coating head from multiple slot manifold assemblies. Inthe case where multiple slot manifold assemblies are used to assemble acoating head, it is advantageous to have a single distribution bladethat is continuous over the entire length of the coating head. However,multiple adjacent or overlapping segments of distribution bladecomprising the length of the coating head are not precluded.

It should be understood that the number of internal pockets and inletports within a slot manifold is variable and may be more or less thanthe two shown in FIG. 4. The number of pockets and inlet ports may beselected to manage the manufacturing complexity of the slot manifold andthe uniformity of flow of coating material from the slot.

In the slot manifold, the wall between internal pockets may be kept asthin as possible. This wall affects the flow of material over the slotlip in its immediate vicinity. By keeping the wall as thin as ispractical, the effect is minimized.

The method of coating using the apparatus may include the followingsteps. First, optionally, the substrate may be prepared for the coatingby increasing the surface energy of the surface to be coated, thusmaking it possible for the coating material to spread evenly on thesubstrate surface by surface tension. In one embodiment, the substrateis glass and the surface energy is increased by washing vigorously withwater and/or mechanical brushes. In other embodiments, the substratesurface may be prepared using gas plasma such as oxygen or by treatmentwith a gas flame. Other pre-treatments are described further herein.

As an initial step, the substrate is pre-treated or pre-cleaned toremove surface impurities and to activate the surface by generating afresh surface or new binding sites on the surface. The substratepre-treatment steps may provide uniform spreading and deposition of thesol, effective bonding interactions between the substrate and coatingmaterial for Si—O—Si linkage formation, and prevention of defects andimperfections at the coating-substrate interface because of unevenspreading and/or diminished bonding interactions due to surfaceinhomogeneities.

In particular, it is desirable to increase the surface energy of thesubstrate through pre-treatment or cleaning of the substrate surface toform an “activated” surface. For example an activated surface may be onewith many exposed Si—OH moieties. An activated surface reduces thecontact angle of the sol and enables effective wetting of the sol on thesurface. In some embodiments, a combination of physical polishing orcleaning and/or chemical etching is sufficient to provide even wettingof the sol. In cases, where the surface tension would need to be furtherlowered, the substrate, such as glass, may be pretreated with a dilutesurfactant solution (low molecular weight surfactants such as surfynol;long chain alcohols such as hexanol or octanol; low molecular weightethylene oxide or propylene oxide; or a commercial dishwasher detergentsuch as CASCADE, FINISH, or ELECTRASOL to further help the sol spreadbetter on the glass surface.

Accordingly, surface preparation may involve a combination of chemicaland physical treatment of the surface. The chemical treatment steps mayinclude (1) cleaning the surface with a solvent or combination ofsolvents, detergents, mild bases like sodium carbonate or ammoniumcarbonate (2) cleaning the surface with a solvent along with an abrasivepad, (3) optionally chemically etching the surface, and (4) washing thesurface with water. The physical treatment steps may include (1)cleaning the surface with a solvent or combination of solvents, (2)cleaning the surface with a solvent along with particulate abrasives,and (3) washing the surface with water. It should be appreciated that asubstrate can be pre-treated by using only the chemical treatment stepsor only the physical treatment steps. Alternatively, both chemical andphysical treatment steps could be used in any combination. It should befurther appreciated that the physical cleaning action of frictionbetween a cleaning brush or pad and the surface may be an importantaspect of the surface preparation.

In the first chemical treatment step, the surface is treated with asolvent or combination of solvents with variable hydrophobicity. Typicalsolvents used are water, ethanol, isopropanol, acetone, and methyl ethylketone. A commercial glass cleaner (e.g., WINDEX) can also be employedfor this purposes. The surface may be treated with an individual solventseparately or by using a mixture of solvents. In the second step, anabrasive pad (e.g., SCOTCHBRITE) is rubbed over the surface with the useof a solvent, noting that this may be performed in conjunction with thefirst step or separately after the first step. In the last step, thesurface is washed or rinsed with water.

One example of substrate preparation by this method involves cleaningthe surface with an organic solvent such as ethanol, isopropanol, oracetone to remove organic surface impurities, dirt, dust, and/or grease(with or without an abrasive pad) followed by cleaning the surface withwater. Another example involves cleaning the surface with methyl ethylketone (with or without an abrasive pad) followed by washing the surfacewith water. Another example is based on using a 1:1 mixture of ethanoland acetone to remove organic impurities followed by washing the surfacewith water.

In some instances an additional, optional step of chemically etching thesurface by means of concentrated nitric acid, sulfuric acid, or piranhasolution (1:1 mixture of 96% sulfuric acid and 30% H₂O₂) may benecessary to make the surface suitable for bonding to the deposited sol.Typically this step would be performed prior the last step of rinsingthe surface with water. In one embodiment, the substrate may be placedin piranha solution for 20 minutes followed by soaking in deionizedwater for 5 minutes. The substrate may then be transferred to anothercontainer holding fresh deionized water and soaked for another 5minutes. Finally, the substrate is rinsed with deionized water andair-dried.

The substrate may alternatively or additionally be prepared by physicaltreatment. In the physical treatment case, the surface may simply becleaned with a solvent and the mechanical action of a cleaning brush orpad, optionally a surfactant or detergent can be added to the solvent,after which the substrate is rinsed with water and air dried. In anotherembodiment, the surface is first cleaned with water followed by additionof powdered abrasive particles such as ceria, titania, zirconia,alumina, aluminum silicate, silica, magnesium hydroxide, aluminumhydroxide particles, silicon carbide, or combinations thereof onto thesurface of the substrate to form a slurry or paste on the surface. Theabrasive media can be in the form a powder or it can be in the form ofslurry, dispersion, suspension, emulsion, or paste. The particle size ofthe abrasives can vary from 0.1 to 10 microns and in some embodimentsfrom 1 to 5 microns. The substrate may be polished with the abrasiveslurry via rubbing with a pad (e.g., a SCOTCHBRITE pad), a cloth, afoam, or paper pad. Alternatively, the substrate may be polished byplacement on the rotating disc of a polisher followed by application ofabrasive slurry on the surface and rubbing with a pad as the substraterotates on the disc. Another alternative method involves use of anelectronic polisher that can be used as a rubbing pad in combinationwith abrasive slurry to polish the surface. The substrates polished withthe slurry are cleaned by pressurized water jet and air-dried.

Next, the substrate to be coated may be positioned with its top edgealigned with and parallel to the bottom edge of the distribution blade.The bottom edge of the distribution blade may overlap slightly with thetop edge of the substrate. The amount of overlap is dependent upon thecoating requirements but may be at least 0.1 mm and in a preferredembodiment be approximately 3 mm. The ends of the distribution blade mayextend slightly beyond the left and right edges of the substrate,between 2 and 100 mm on each side. In an embodiment, it extends by 10 mmon each side. The substrate may be inclined at an angle of 60° to 85°relative to horizontal. In the case of a flexible thin distributionblade, the angle between the surface of the substrate and the surface ofthe distribution blade may be between 0° and 5°. The substrate can bepushed slightly against the distribution blade to apply pressure to thecontact area such that the distribution blade conforms to any grossirregularity or deviation from flatness of the substrate. In the case ofa rigid distribution blade, the substrate may be positioned with itsfront surface parallel to the back surface of the distribution blade anda clamping mechanism may hold the substrate to the distribution bladesuch that any warping or deviation from flatness of the substrate iseliminated against the flat back side of the distribution blade. In oneembodiment, the coating head is stationary and the substrate is broughtto it. However, in other embodiments, the substrate may be stationaryand the coating head moved to position or both elements may movetogether to arrive at the final coating position. It is also possiblefor both elements to be stationary relative to each other but to bemoving relative to the larger coating system.

Next, the front surface of the substrate may be completely wetted with apre-wet solution. This pre-wet solution is dispensed in a manner thatquickly wets the entire substrate surface rapidly, such as in less than30 seconds. In one embodiment, a plurality of fan nozzles positioned ona rotatable mechanism above and in front of the substrate and along itslength aligned to the coating head starts spraying pre-wet solution suchthat it first wets the distribution blade along it entire length. Thenthe nozzle assembly rotates such that the fan shaped jets of pre-wetsolution from the nozzles travel down the substrate from its top edge toits bottom edge and in the process deposit pre-wet solution on the fullsurface of the distribution blade and the substrate. When employed, thepre-wet step decreases the time for the coating material to completelywet the substrate to between 1 and 25 seconds; improves the uniformityof distribution of the coating material on the substrate to ±25% byvolume per unit area and reduces the amount of coating material neededto completely coat the substrate by up to 90%. The composition of thepre-wet solution is chosen to provide a number of properties: Theviscosity is within ±50% of the viscosity of the coating material andmore preferably within ±10% and even more preferably within ±2% and/orthe surface tension is within ±50% of the surface tension of the coatingmaterial and more preferably within ±10% and even more preferably within±2% and/or the vapor pressure is within ±50% of the vapor pressure ofthe coating material and more preferably within ±10% and even morepreferably within ±2%. In one embodiment, the pre-wet solution comprisesthe same mixture of solvents, mixed in the same ratios as the coatingmaterial. For example, the pre-wet solution might be composed of 90%isopropyl alcohol and 10% water that approximately matches the ratio ofisopropyl alcohol and water in a sol-gel coating material. In analternative embodiment, the pre-wet solution could be a non-ionic,cationic or anionic surfactant, such as for example Sodium dodecylsulfate or perfluoroalkyl sulfonate.

Next or some time shortly after the pre-wet step has commenced, apre-determined amount of coating material may be dispensed from thecoating head on to the substrate. The coating material flows down thesubstrate completely covering the front surface of the substrate. Excesscoating material may drip from the bottom edge or be wicked away frombottom edge by capillary action onto a mechanism designed for thatpurpose. In some embodiments, excess coating material may be collectedat the bottom of the substrate for reuse. The decision to reuse thismaterial or not depends on the composition of the coating material andsubstrate. For example, if the coating material is quite stable and doesnot significantly change during the time it travels down the substrateand if the substrate does not contaminate the coating material then adecision might be made to reuse excess material collected from thebottom edge.

Next, optionally, there may be a pause of between 1 and 600 secondsafter the dispensing of coating material has finished while excesscoating material is able to drain out of the internal pocket and fromthe wet surface of the distribution blade onto the substrate. The lengthof this pause may be optimized to reduce the possibility of drips fromthe distribution blade after the substrate is removed from the coatinghead. In some embodiments, this pause may be long enough to allow thedistribution blade and/or the top area of the substrate to dry orpartially dry.

Next, the substrate may be withdrawn from the coating head. In someembodiments, if the coating head is still wet, a drip guard may quicklymove into place between the substrate and the bottom edge of thedistribution blade. This drip guard may optionally touch the bottom edgeof the blade to wick away excess material in which case the surface ofthe drip guard may have similar surface characteristics to the frontsurface of the distribution blade to encourage the coating material toeasily flow off the distribution blade.

Finally, the substrate may be allowed to dry in a manner that allows thecoating material to undergo gelation such that a uniform high qualitycoating is formed on the substrate surface.

This coating method, enabled by the novel design of the coating head canhave several of the following advantages over alternative coatingtechniques. First, by dispensing material simultaneously across the fullwidth of the substrate the time to dispense can be greatly shortened.Second, by pre-wetting the substrate the amount of time for the coatingmaterial to flow down the substrate can be greatly shortened and theamount of coating material required to fully wet the substrate surfaceis greatly reduced. Third, if coating material is not collected at thebottom of the substrate for reuse then only fresh (virgin) material canbe deposited on the substrate so control of coating material purity andcomposition can be greatly increased. Fourth, by utilizing adistribution blade in conjunction with a properly sized slot dispenser,the uniformity of flow of material on to the substrate can be greatlyincreased at very low cost and with a very simply system. Fifth, thetechnique can be very tolerant of deviation of flatness on the substratewithout requiring any precision mechanical control or design. Sixth, themethod does not necessarily pose any significant chemical compatibilitychallenges where it may be difficult to identify critical coatingcomponents with properties that are not sensitive to or contaminate thecoating material. Finally, the method can be inherently single sidedallowing the flexibility to coat one side of the substrate or both (in asecond coating step) if needed.

Is should also be understood that in some embodiments the formulation ofthe coating material will have a significant effect on the uniformity ofthe thin-film. In particular, in a sol-gel coating material the ratio ofsolids or particle content to solvent in conjunction with the ambientconditions during drying may affect the gelation process that occurs asthe thin-film forms. Careful control of these elements will enhance theuniformity of the final thin-film especially in the top to bottomdirection on the substrate.

FIG. 7 a shows a simplified schematic of a forward roll coatingapparatus. FIG. 7 b shows a simplified schematic of a reverseroll-coating apparatus. In both figures, a flat substrate (160) is fedfrom left to right. A counter pressure roller (163) supports thesubstrate from the bottom and moves in a complementary direction to themovement of the substrate. A coating material (164) is deposited in areservoir created between a doctor roller (162) and an applicationroller (161). The pressure or spacing of the doctor roller toapplication roller controls the amount of coating material that istransferred to the application roller. The surfaces of the doctor andapplication rollers may be smooth or textured, soft or hard. The rollersurfaces need not be the same. For example, the doctor roller may becompliant and textured while the application roller could be hard andsmooth and vice versa. The application roller transfers coating materialto the surface of the substrate. The pressure or distance between theapplication roller and the substrate surface is adjustable to facilitatecontrol of the final wet-coating thickness and/or uniformity of thematerial on the substrate. In forward roll-coating, the applicationroller (161) moves in the same direction as the direction of motion ofthe substrate. In reverse roll-coating, the application roller (161)moves in the opposite direction to the motion of the substrate.

The substrate may be continuous, such as for example a roll of polymersheet or steel, or it may be discontinuous, such as discrete pieces ofglass or wood or individual solar panels. In the case of discontinuoussubstrates, the application roller assembly may be moved in a verticaldirection such that it touches down on the leading edge of the substrateas it enters the roll-coater and then lifts off the trailing edge as thesubstrate exits the roll-coater. This technique may reduce uniformity onthe leading and trailing edges.

Selection of the materials within the roll-coater that come into contactwith the liquid coating material are a consideration. In someembodiments, the coating material may be corrosive, having either a highor low pH. In an embodiment, the pH of the coating material is between1.8 and 2.8. Additionally, in some embodiments, the coating materialcontains organic solvents such as iso-propyl alcohol, methanol, ethanol,propylene glycol monomethyl ether, propylene glycol monomethyl etheracetate, and the like. All materials may be selected to withstand boththe organic solvents and pH conditions used. For metallic components,stainless steel is preferential with chrome-plated steel, for example.In selecting polymer materials for pipes, fittings and seals made frompolytetrafluoroethylene, polypropylene, polyether ether ketone, andpolyvinylidene difluoride may be considered. For polymer coatings on therollers polyurethane, EPDM (ethylene propylene diene monomer) rubber andnitrile rubber are suitable. The particular embodiment of a roll-coaterselected for a specific sol-gel coating application depends upon anumber of factors. The wet film thickness is a process parameter toconsider in achieving the final cured film thickness. The desired wetthickness may be dependent on the desired final dry thickness, thesolids content of the coating material and the target porosity of thefinal dry film. In one embodiment, the desired final thickness is 120 nm(DT), the solids content (SC) of the coating material is between 1% and3% by volume and the target porosity (P) is 10%. The target wetthickness (WT) may be calculated with the following formula:

${WT} = \frac{DT}{{SC}*\left( {1 - P} \right)}$

For example, the equation yields a target wet thickness betweenapproximately 4 μm and 14 μm using the input parameters above. Wetthickness can be controlled by a number of process controls on theroll-coater system. Selection of which parameters are most important isdependent upon the characteristics of the coating material, such as forexample its viscosity, and the architecture or operation mode of theroll-coater, such as forward or reverse. Typically, the parametersadjusted are the doctor roller spacing and/or pressure to theapplication roller; the application roller spacing/pressure to thesubstrate; the speed at which the substrate moves and in the case ofreverse roll-coating the difference in speed between the substrate andthe application roller. The speed at which the doctor roller movesrelative to the application roller is also a process parameter. FIG. 8shows an embodiment of a roll-coater used for sol-gel coating of flatsubstrates such as glass or solar panels. The roll-coater (170) ispositioned after a feed-in conveyor (171) and ahead of a feed-outconveyor (172). In FIG. 8, substrates move from right to left. Coatingmaterial (173) is fed to the roll-coater from a storage tank at acontrolled rate by a pump (174). Excess material is collected (177) offthe ends of the rollers and recirculated. An optional pre-heater (175)may be positioned such that it can heat the substrate prior to theroll-coater. The substrate may be heated to a temperature, such as atemperature between 2° C. and 80° C. In some embodiments, this pre-heatstep can serve to reduce thermal stress during the very rapid heating ofsubsequent process step. In other embodiments, it is used to controlevaporation rates of the coating material placed on the substrate toachieve specific process targets such as uniformity, film-thickness,porosity or process speed. Careful consideration should be paidregarding heat transfer from warmed substrates to the application rollersuch that it is accounted for in the process. In one embodiment, aflash-off heater (176) is positioned at the output of the roll-coater tocontrol evaporation of the solvent of the coating material to facilitatethe gelation of the thin-film. In some embodiments, the pre-heater andthe flash-off heater may be radiant infra-red or in other embodimentsthey may be electric or fuel fired convection heaters. In anotherembodiment forced air at ambient or close to ambient temperature couldbe used to accomplish the flash-off process by accelerating solventevaporation.

The conveyor systems used to move substrates between process stages maybe continuous belt driven systems. In some embodiments robots might beused to convey substrates between process stages. In other embodimentsubstrates might be conveyed by humans using carts. In any case itshould be understood that substrates may be conveyed between processsteps by many means known in the art.

An important consideration when using roll-coaters is accommodating orcontrolling for evaporation of coating material solvent from theequipment itself as the machine is running. To mitigate thisevaporation, it can be advantageous to add make-up solvent to thecoating material such that the solids concentration is controlled withina workable range. Make-up solvent can be added at a constant rate knownto match the steady-state rate of evaporation; it can be addedperiodically based on pre-determined intervals based on time, quantitiesof substrates coated, or coating material consumed. Make-up solvent canbe added based on an active feedback loop wherein the solidsconcentration is measured directly or indirectly and then used tocontrol the amount added. Solids concentration might be measured byoptical means such as dynamic light scattering or adsorption orrefractive index; it could be measured by physical properties such asfor example density or viscosity; it could be measured chemically suchas for example monitoring pH.

Sol-gel materials used for coatings are often sensitive to environmentalconditions such as relative humidity and temperature during the gelationprocess. Additionally, sol-gel materials may release significant amountsof solvent vapor prior to or during cure. It is therefore desirable toengineer the environment around the roll-coating system such as thattemperature and humidity are controlled, and solvent vapor is removed.In some embodiments a containment chamber is built around the completeroll-coater system with a dedicated HVAC unit to control temperature andrelative humidity. In an embodiment, there is a secondary interiorcontainment around the coater application roller and the flash-off areathat is small in volume such that its temperature and relative humiditycan be controlled more easily. This interior containment area is alsoused to collect solvent vapor for venting, destruction or recycling.This has an additional advantage to prevent people working inside theprimary containment area from being subjected to elevated levels ofsolvent vapor. Such an environmental chamber system would have safetyinterlocks such that the tool could be stopped and any coating materialsafely contained if the solvent vapors approached flammability safetylimits.

FIG. 9 shows a cross-sectional schematic view of one embodiment of acuring apparatus and method for skin-cure. In this apparatus, anair-knife (180) directs heated air on to the surface of a substrate(181) presented to the air-knife by a feed-in conveyor (182) andextracted by a feed-out conveyor (183). The air may be heated by anelectrical element (184), as shown in FIG. 9, may also be heated by anyother method known in the art. The air may be heated to any temperatureuseful in the method, such as to a temperature of 300° C. to 1000° C.Air may be forced through the heating element and air-knife by a fan(185). The temperature of the air is controlled by an electroniccontroller (186) and temperature sensor (188) located in the heated airstream. Optionally, overheat protection of the heating element may beprovided by the electronic controller and, optionally, a secondtemperature sensor (187) located close to the heating element. When nosubstrate is present, air may flow from the fan through the heatingelement, through the air-knife and then directly to the exhaust (197).When a substrate is present, the air flows along the top surface of thesubstrate. In an embodiment, a pre-heating stage (189), for example aninfra-red emitter, heats the substrate prior to the air-knife. Thepre-heat temperature is controlled by an electronic controller (190) anda temperature sensor (191) with an optional safety over-heat sensor(192). In another embodiment a flat plate attached to the leading edgeof the air-knife forms a pre-heat chamber (189) with the top surface ofsubstrate. This pre-heat chamber traps the hot air close to thesubstrate surface for a longer period allowing the hot air more time topre-heat the substrate surface. A post-heating stage (193), for examplean infra-red emitter (190), located subsequent to the air-knife providesadditional heat that can extend the time that the substrate stays at anelevated temperature. The post-heating temperature is controlled by anelectronic controller (194) and a temperature sensor (195), with anoptional safety over-heat sensor (196). In another embodiment, there isa heating element in place of the pre-heat chamber. The pre-heating ofthe substrate can serve to reduce thermal stress during the very rapidheating under the air-knife and to provide an additional control on thepeak temperature the substrate reaches under the air-knife, the peaktemperature being a function of the initial temperature plus thetemperature rise due to the air-knife.

A major advantage of this embodiment of a skin-cure system is that itallows the curing of a thin-film sol-gel coating without heating theentire substrate to a high temperature. A properly configured air-knifeis able to heat the surface very fast (high power) without imparting agreat deal of heat (energy) to the full substrate. Thus while thesurface heats rapidly to a high temperature the overall substrate doesnot heat up excessively. In one embodiment the substrate is glass coatedon one side with thin-film solar cells, and the opposing side of theglass is the desired surface for the sol coating. In this case, it isdesirable to avoid heating and raising the temperature of thesemiconductor photovoltaic material as much as possible while curing thesol coating. Thin-film solar materials such as CdTe, CIGS or amorphoussilicon can be quite sensitive to elevated temperatures. Hightemperatures can cause dopants within the material to defuse in adetrimental manner or can cause metal electrode materials to defuse intothe photovoltaic material. In some embodiments, the temperature of thephotovoltaic cell may be kept from exceeding 100° C. to 120° C. as thesol is cured. Additionally, polymer materials within the finished solarpanel such as encapsulates may be kept from exceeding their glasstransition temperature of 150° C. to 200° C.

FIG. 10 shows an example temperature profile for a skin-cure system. Inthis example the substrate is a dummy thin-film solar module consistingof two pieces of glass typical of those used in thin-film modulemanufacturing, laminated together with temperature sensors embeddedbetween the glass sheets such that they measure the interior temperatureof the dummy module and temperature sensors attached to the top surface.The module was moved at a speed of 1 cm/s under an air-knife set to anexit air temperature of approximately 650° C. and a gap distance (fromsubstrate top surface to the air-knife opening) of approximately lcm.Two temperatures are shown, the top surface temperature representing thetemperature reached by the interior of the dummy module. In this examplethe pre-heat chamber embodiment was used. From the profile, the pre-heatchamber caused an initial rise in temperature of the top surface (202)to approximately 100° C., there after the air-knife caused a very rapidtemperature rise (200) to approximately 300° C. after which thepost-heat infra-red emitter set to a temperature of 300° C. as measuredby a sensor placed between the substrate and the IR emitter, maintainsthe top surface temperature (201) at approximately 200° C. Through-outthe process the interior temperature never exceeds approximately 90° C.

In one embodiment, the substrate is glass of thickness 1 mm to 4 mm. Inan embodiment of a skin-cure apparatus, the air-temperature exiting theair knife is between 500° C. to 750° C. as controlled by the powersetting of the heating element and the volume of air provided by thefan. The speed of the substrate is between 0.25 cm/s and 3.5 cm/s. Theresulting temperature of the substrate surface is between 150° C. to600° C. and this temperature is attained between the start of thepre-heat chamber and the end of the air-knife. In other embodiments thesubstrate is pre-heated by an infra-red emitter to approximately 25° C.to 200° C. prior to the air-knife wherein it is further heated toapproximately 150° C. to 600° C. Thereafter, the substrate is maintainedat a temperature of between 120° C. to 400° C. until the end of thepost-heat section. Such a configuration of the skin-cure apparatus hasbeen shown to cure the sol coating while leaving the opposing surface ata temperature below 120° C.

The process of rapidly heating the substrate using the air-knife andthen maintaining that temperature with radiant heat facilitates thecuring of the sol-gel material. In an embodiment, the curing is achievedby providing sufficient energy so that a sufficient portion of theremaining Si—OH moieties within the coating undergo a condensationreaction and form Si—O—Si crosslinks that greatly strengthen thematerial enabling it to pass Taber abrasion testing to standardEN-1096-2 with no more than 0.5% loss of absolute transmission. In otherembodiments, the curing temperature is used to facilitate otherprocesses such as volatizing a sacrificial component of the coating toform a desired porosity or a desired surface morphology. Otherembodiments may use very high temperatures to completely oxidize allorganic components in the coating creating a hydrophilic pure silicafilm. Yet further embodiments may use the heat and/or reactive gascomposition of the air-knife to initiate chemical reactions that modifythe properties of the coating, such as for example, surface energy,color, refractive index, surface morphology and surface chemistry. Inembodiments, the skin-cure process works in concert with the compositionand properties of the coating material to facilitate tuning of theproperties of the final thin-film coating.

FIG. 11 shows a thermogravimetric analysis of representative samples ofcoating material. Thermogravimetric analysis is performed by heating asample gradually and recording the loss of mass as various components ofthe sample volatize. When performed on coating materials such as theseexample sol-gel coatings for glass, it can be used to determine criticaltemperatures required to cure the coating material. The figure showsthree temperatures of interest. Using Sample 1 in FIG. 11 as anillustrative example, there is a point of inflection (210) atapproximately 125° C., another much steeper point of inflection (211) atapproximately 450° C. finally there is a flattening out (212) above 500°C. Without being bound by theory, these three points are interpreted asfollows. As temperature increases to point 210 any residual water andsolvent is volatilized and all easily accessible Si—OH moieties reactand release water. This represents a substantially cured film that hasattained a useful hardness and abrasion resistance at a relatively lowtemperature. Further heating in the range from point 210 until point 211represents an approximately linear reduction in mass as additionalremaining Si—OH moieties condense and release water. This temperaturerange represents increasing hardness and abrasion resistance of thematerial with increasing temperature, without detrimental effects on thecoating. This reduction in mass causes a corresponding decrease indensity and hence a decrease in refractive index. In coating materialsthat form hydrophobic films, the reduction in Si—OH will also result inan increase of the hydrophobic effect as measured by increasing watercontact angle. Heating beyond point 211 begins to oxidize organicmoieties within the coating, the byproducts of which may thenvolatilize. In some embodiments these moieties may be methyl groups orother hydro-carbon groups or fluoro-carbon chains or any combinationthereof. Other reactions may also occur such as for example theformation of SiC and SiOC. This temperature regime may be generalized asthe oxidation of the organic components of the coating, reactionsbetween byproducts of that oxidation with each other and with componentsof the film itself and the transformation of the coating to asubstantially inorganic silica coating. At this point further heating nolonger causes significant mass loss and the curve flattens out asindicated by point 212. Sample 2 is a different sol-gel coating materialfor glass, however, it also exhibits approximately the same shape andinflection points as Sample 1. It also illustrates that when morecomplex organic moieties are present in the coating the transformationthat occurs after the second inflection point can be more complex andmore prolonged. Therefore for the purposes of developing a process forcuring these coatings we can determine from this analysis that a firstlow temperature cure can be accomplished at a temperature ofapproximately 125° C., that is the first point of inflection. A secondhigher temperature cure at the second point of inflection (approximately450° C. for the material in Sample 1 and 350° C. for the material inSample 2) results in increased hardness, abrasion resistance andhydrophobicity. Temperatures beyond the second inflection point resultin the breakdown and modification of organic moieties that may in someembodiments be useful.

The curing process parameters including substrate speed, air knifeoutput air temperature, air knife air flow volume, air knife openingdistance to substrate surface, pre and post heating set temperatures areused to control process cure parameters including maximum temperature,rate of heating, duration at temperature, cumulative temperatureexposure and rate of cooling that can be used to tune specificproperties of the final cured film. One property is hardness as measuredby nanoindentation methods. In some embodiments, the curing systemdescribed herein may cure sol-gel coatings on glass substrates to ahardness of approximately 0.2 GPa to 10 GPa and preferably to a hardnessof approximately 2 GPa to 4 GPa. Another property is abrasionresistance. In some embodiments, the curing system described herein maycure sol-gel coatings on glass substrates to an abrasion resistancewhereby they lose no more than 1% of absolute optical transmission asmeasured by spectrophotometer after 500 strokes of an abrasion testperformed in accordance with specification EN1096-2 and preferably nomore than 0.5% loss of absolute optical transmission after 1000 strokes.Such a test can be performed using a Taber reciprocating abrader model5900 with a ratcheting arm assembly. A third property is surface energyas measured by water contact angle (WCA). In some embodiments the curingsystem described herein may cure sol-gel coatings to a WCA ofapproximately 60° to 120° and preferably to a WCA of approximately 70°to 100°. In other embodiments the film can be cured to a WCA ofapproximately 5° to 30° and preferably a WCA of approximately 10° to20°. A fourth property is refractive index (RI) as measured byellipsometer. In some embodiments curing system described herein maycure sol-gel coatings to a RI of approximately 1.25 to 1.45 andpreferably a RI of approximately 1.35 to 1.42. A fifth property is finalfilm thickness as measured by ellipsometer. The final film thickness isa function of the initial (pre-cure) dry film thickness and the cureparameters such that the cure parameters modify the initial drythickness. In some embodiments the curing system described herein maycure sol-gel coatings to a thickness of 50 nm to 150 nm and to apreferred thickness of 70 nm to 130 nm.

FIGS. 12 a, FIG. 12 b and FIG. 12 c depict data for an exemplary sol-gelcoating that demonstrate control of final film thickness, refractiveindex and water contact angle as a function of maximum cure temperature.

FIG. 13 shows Fourier transform infrared spectroscopy data for anexemplary sol-gel coating material taken before and after a cure processstep. This analysis technique shows how chemical bonds within thematerial change during the curing process. In particular the spectralpeaks denoted by points 220, 221 & 222 have changed during the process.Without being bound by theory, these changes can be interpreted as thereduction of Si—OH bonds through condensation causing the reduction ofthe peaks at points 220 and 222. These bonds are converted to Si—O—Sibonds causing the increase in the peak at point 221. This analysistechnique can be used to quantify the proportion of Si—OH bonds thatcondense and hence to quantify the degree to which the film is cured.

The coating and curing process steps may further be configured in tocreate coatings of varying complexity and structure. In embodiments, anycombination of coating technique and curing technique may be used toachieve a final coating for a substrate. Embodiments of suchcombinations may include coating via a flow coating technique followedby a skin cure process or cure by conventional means, coating via a rollcoating technique followed by a skin cure process or cure byconventional means, and the like. To generate multilayer coatings, anycombination of coating and curing apparatus may be used sequentially togenerate such a coating. The sequential use of such apparatus may beenabled by an arrangement that places multiple coating apparatus andcuring apparatus in sequence. Alternatively, handling facilities mayexist for handling the substrate between one or more coating and curingapparatus. For example, two roll-coaters may be placed in sequence withan optional flash-off heater in between. This facilitates coating of afirst layer by the first roll-coater, drying of the layer by theflash-off station, then deposition of a second layer by the secondroll-coater before curing in a skin-cure station or in a simple oven.Alternatively, a high temperature skin-cure step may be interposedbetween the roll-coaters to enable a high temperature heat treatment tothe first layer before application of the second layer. It is understoodthat this technique for multiple layer coatings may be extended to morethan two layers. Multi-layer coatings manufactured by this technique maybe high performance anti-reflective interference type coatings ormultiple layers coatings could be used to modify the surface energy ofthe top surface coating by for example adding a fluorinated silanemono-layer to an underlying layer to make the final coating hydrophobicand oleophobic on the environmentally exposed surface. The multi-layercoatings may be used to enhance single layer anti-reflective coatings byadding a lower refractive index material on the environmentally exposedsurface to create a graded index coating between the environment and theunderlying substrate.

The foregoing apparatus and methods are particularly well suited to theapplication of sol-gel thin-films to glass. In an embodiment, the glassto be coated is the front (sun facing) surface of a solar panel and thesol-gel thin-film is an anti-reflective coating. Either bare glass maybe coated and/or cured by the apparatus or fully assembled solar panelsor solar panels at any intermediate stage of manufacture. In otherembodiments, the apparatus may be used to coat and/or cure windows,architectural glass, displays, lenses, mirrors or other electronicdevices.

Embodiments described herein are well suited to performing various othersteps or variations of the steps recited herein, and in a sequence otherthan that depicted and/or described herein.

It should be appreciated that reference throughout this specification to“one embodiment” or “an embodiment” means that a particular feature,structure or characteristic described in connection with the embodimentis included in at least one embodiment of the present disclosure.Therefore, it is emphasized and should be appreciated that two or morereferences to “an embodiment” or “one embodiment” or “an alternativeembodiment” in various portions of this specification are notnecessarily all referring to the same embodiment. Furthermore, theparticular features, structures or characteristics may be combined assuitable in one or more embodiments of the disclosure.

Similarly, it should be appreciated that in the foregoing description ofexemplary embodiments of the disclosure, various features of thedisclosure are sometimes grouped together in a single embodiment,figure, or description thereof for the purpose of streamlining thedisclosure aiding in the understanding of one or more of the variousinventive aspects. This method of disclosure, however, is not to beinterpreted as reflecting an intention that the claimed disclosurerequires more features than are expressly recited in each claim. Rather,as the following claims reflect, inventive aspects lie in less than allfeatures of a single foregoing disclosed embodiment. Thus, the claimsfollowing the detailed description are hereby expressly incorporatedinto this detailed description, with each claim standing on its own as aseparate embodiment of this disclosure.

While only a few embodiments of the present disclosure have been shownand described, it will be obvious to those skilled in the art that manychanges and modifications may be made thereunto without departing fromthe spirit and scope of the present disclosure as described in thefollowing claims. All patent applications and patents, both foreign anddomestic, and all other publications referenced herein are incorporatedherein in their entireties to the full extent permitted by law.

The methods and systems described herein may be deployed in part or inwhole through a machine that executes computer software, program codes,and/or instructions on a processor. The present disclosure may beimplemented as a method on the machine, as a system or apparatus as partof or in relation to the machine, or as a computer program productembodied in a computer readable medium executing on one or more of themachines. In embodiments, the processor may be part of a server, cloudserver, client, network infrastructure, mobile computing platform,stationary computing platform, or other computing platform. A processormay be any kind of computational or processing device capable ofexecuting program instructions, codes, binary instructions and the like.The processor may be or may include a signal processor, digitalprocessor, embedded processor, microprocessor or any variant such as aco-processor (math co-processor, graphic co-processor, communicationco-processor and the like) and the like that may directly or indirectlyfacilitate execution of program code or program instructions storedthereon. In addition, the processor may enable execution of multipleprograms, threads, and codes. The threads may be executed simultaneouslyto enhance the performance of the processor and to facilitatesimultaneous operations of the application. By way of implementation,methods, program codes, program instructions and the like describedherein may be implemented in one or more thread. The thread may spawnother threads that may have assigned priorities associated with them;the processor may execute these threads based on priority or any otherorder based on instructions provided in the program code. The processor,or any machine utilizing one, may include memory that stores methods,codes, instructions and programs as described herein and elsewhere. Theprocessor may access a storage medium through an interface that maystore methods, codes, and instructions as described herein andelsewhere. The storage medium associated with the processor for storingmethods, programs, codes, program instructions or other type ofinstructions capable of being executed by the computing or processingdevice may include but may not be limited to one or more of a CD-ROM,DVD, memory, hard disk, flash drive, RAM, ROM, cache and the like.

A processor may include one or more cores that may enhance speed andperformance of a multiprocessor. In embodiments, the process may be adual core processor, quad core processors, other chip-levelmultiprocessor and the like that combine two or more independent cores(called a die).

The methods and systems described herein may be deployed in part or inwhole through a machine that executes computer software on a server,client, firewall, gateway, hub, router, or other such computer and/ornetworking hardware. The software program may be associated with aserver that may include a file server, print server, domain server,internet server, intranet server, cloud server, and other variants suchas secondary server, host server, distributed server and the like. Theserver may include one or more of memories, processors, computerreadable media, storage media, ports (physical and virtual),communication devices, and interfaces capable of accessing otherservers, clients, machines, and devices through a wired or a wirelessmedium, and the like. The methods, programs, or codes as describedherein and elsewhere may be executed by the server. In addition, otherdevices required for execution of methods as described in thisapplication may be considered as a part of the infrastructure associatedwith the server.

The server may provide an interface to other devices including, withoutlimitation, clients, other servers, printers, database servers, printservers, file servers, communication servers, distributed servers,social networks, and the like. Additionally, this coupling and/orconnection may facilitate remote execution of program across thenetwork. The networking of some or all of these devices may facilitateparallel processing of a program or method at one or more locationwithout deviating from the scope of the disclosure. In addition, any ofthe devices attached to the server through an interface may include atleast one storage medium capable of storing methods, programs, codeand/or instructions. A central repository may provide programinstructions to be executed on different devices. In thisimplementation, the remote repository may act as a storage medium forprogram code, instructions, and programs.

The software program may be associated with a client that may include afile client, print client, domain client, internet client, intranetclient and other variants such as secondary client, host client,distributed client and the like. The client may include one or more ofmemories, processors, computer readable media, storage media, ports(physical and virtual), communication devices, and interfaces capable ofaccessing other clients, servers, machines, and devices through a wiredor a wireless medium, and the like. The methods, programs, or codes asdescribed herein and elsewhere may be executed by the client. Inaddition, other devices required for execution of methods as describedin this application may be considered as a part of the infrastructureassociated with the client.

The client may provide an interface to other devices including, withoutlimitation, servers, other clients, printers, database servers, printservers, file servers, communication servers, distributed servers andthe like. Additionally, this coupling and/or connection may facilitateremote execution of program across the network. The networking of someor all of these devices may facilitate parallel processing of a programor method at one or more location without deviating from the scope ofthe disclosure. In addition, any of the devices attached to the clientthrough an interface may include at least one storage medium capable ofstoring methods, programs, applications, code and/or instructions. Acentral repository may provide program instructions to be executed ondifferent devices. In this implementation, the remote repository may actas a storage medium for program code, instructions, and programs.

The methods and systems described herein may be deployed in part or inwhole through network infrastructures. The network infrastructure mayinclude elements such as computing devices, servers, routers, hubs,firewalls, clients, personal computers, communication devices, routingdevices and other active and passive devices, modules and/or componentsas known in the art. The computing and/or non-computing device(s)associated with the network infrastructure may include, apart from othercomponents, a storage medium such as flash memory, buffer, stack, RAM,ROM and the like. The processes, methods, program codes, instructionsdescribed herein and elsewhere may be executed by one or more of thenetwork infrastructural elements. The methods and systems describedherein may be adapted for use with any kind of private, community, orhybrid cloud computing network or cloud computing environment, includingthose which involve features of software as a service (SaaS), platformas a service (PaaS), and/or infrastructure as a service (IaaS).

The methods, program codes, and instructions described herein andelsewhere may be implemented on a cellular network having multiplecells. The cellular network may either be frequency division multipleaccess (FDMA) network or code division multiple access (CDMA) network.The cellular network may include mobile devices, cell sites, basestations, repeaters, antennas, towers, and the like. The cell networkmay be a GSM, GPRS, 3G, EVDO, mesh, or other networks types.

The methods, program codes, and instructions described herein andelsewhere may be implemented on or through mobile devices. The mobiledevices may include navigation devices, cell phones, mobile phones,mobile personal digital assistants, laptops, palmtops, netbooks, pagers,electronic books readers, music players and the like. These devices mayinclude, apart from other components, a storage medium such as a flashmemory, buffer, RAM, ROM and one or more computing devices. Thecomputing devices associated with mobile devices may be enabled toexecute program codes, methods, and instructions stored thereon.Alternatively, the mobile devices may be configured to executeinstructions in collaboration with other devices. The mobile devices maycommunicate with base stations interfaced with servers and configured toexecute program codes. The mobile devices may communicate on apeer-to-peer network, mesh network, or other communications network. Theprogram code may be stored on the storage medium associated with theserver and executed by a computing device embedded within the server.The base station may include a computing device and a storage medium.The storage device may store program codes and instructions executed bythe computing devices associated with the base station.

The computer software, program codes, and/or instructions may be storedand/or accessed on machine readable media that may include: computercomponents, devices, and recording media that retain digital data usedfor computing for some interval of time; semiconductor storage known asrandom access memory (RAM); mass storage typically for more permanentstorage, such as optical discs, forms of magnetic storage like harddisks, tapes, drums, cards and other types; processor registers, cachememory, volatile memory, non-volatile memory; optical storage such asCD, DVD; removable media such as flash memory (e.g. USB sticks or keys),floppy disks, magnetic tape, paper tape, punch cards, standalone RAMdisks, Zip drives, removable mass storage, off-line, and the like; othercomputer memory such as dynamic memory, static memory, read/writestorage, mutable storage, read only, random access, sequential access,location addressable, file addressable, content addressable, networkattached storage, storage area network, bar codes, magnetic ink, and thelike.

The methods and systems described herein may transform physical and/oror intangible items from one state to another. The methods and systemsdescribed herein may also transform data representing physical and/orintangible items from one state to another.

The elements described and depicted herein, including in flow charts andblock diagrams throughout the figures, imply logical boundaries betweenthe elements. However, according to software or hardware engineeringpractices, the depicted elements and the functions thereof may beimplemented on machines through computer executable media having aprocessor capable of executing program instructions stored thereon as amonolithic software structure, as standalone software modules, or asmodules that employ external routines, code, services, and so forth, orany combination of these, and all such implementations may be within thescope of the present disclosure. Examples of such machines may include,but may not be limited to, personal digital assistants, laptops,personal computers, mobile phones, other handheld computing devices,medical equipment, wired or wireless communication devices, transducers,chips, calculators, satellites, tablet PCs, electronic books, gadgets,electronic devices, devices having artificial intelligence, computingdevices, networking equipment, servers, routers and the like.Furthermore, the elements depicted in the flow chart and block diagramsor any other logical component may be implemented on a machine capableof executing program instructions. Thus, while the foregoing drawingsand descriptions set forth functional aspects of the disclosed systems,no particular arrangement of software for implementing these functionalaspects should be inferred from these descriptions unless explicitlystated or otherwise clear from the context. Similarly, it will beappreciated that the various steps identified and described above may bevaried, and that the order of steps may be adapted to particularapplications of the techniques disclosed herein. All such variations andmodifications are intended to fall within the scope of this disclosure.As such, the depiction and/or description of an order for various stepsshould not be understood to require a particular order of execution forthose steps, unless required by a particular application, or explicitlystated or otherwise clear from the context.

The methods and/or processes described above, and steps associatedtherewith, may be realized in hardware, software or any combination ofhardware and software suitable for a particular application. Thehardware may include a general-purpose computer and/or dedicatedcomputing device or specific computing device or particular aspect orcomponent of a specific computing device. The processes may be realizedin one or more microprocessors, microcontrollers, embeddedmicrocontrollers, programmable digital signal processors or otherprogrammable device, along with internal and/or external memory. Theprocesses may also, or instead, be embodied in an application specificintegrated circuit, a programmable gate array, programmable array logic,or any other device or combination of devices that may be configured toprocess electronic signals. It will further be appreciated that one ormore of the processes may be realized as a computer executable codecapable of being executed on a machine-readable medium.

The computer executable code may be created using a structuredprogramming language such as C, an object oriented programming languagesuch as C++, or any other high-level or low-level programming language(including assembly languages, hardware description languages, anddatabase programming languages and technologies) that may be stored,compiled or interpreted to run on one of the above devices, as well asheterogeneous combinations of processors, processor architectures, orcombinations of different hardware and software, or any other machinecapable of executing program instructions.

Thus, in one aspect, methods described above and combinations thereofmay be embodied in computer executable code that, when executing on oneor more computing devices, performs the steps thereof. In anotheraspect, the methods may be embodied in systems that perform the stepsthereof, and may be distributed across devices in a number of ways, orall of the functionality may be integrated into a dedicated, standalonedevice or other hardware. In another aspect, the means for performingthe steps associated with the processes described above may include anyof the hardware and/or software described above. All such permutationsand combinations are intended to fall within the scope of the presentdisclosure.

While the disclosure has been disclosed in connection with the preferredembodiments shown and described in detail, various modifications andimprovements thereon will become readily apparent to those skilled inthe art. Accordingly, the spirit and scope of the present disclosure isnot to be limited by the foregoing examples, but is to be understood inthe broadest sense allowable by law.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the disclosure (especially in the context of thefollowing claims) is to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. All methodsdescribed herein can be performed in any suitable order unless otherwiseindicated herein or otherwise clearly contradicted by context. The useof any and all examples, or exemplary language (e.g., “such as”)provided herein, is intended merely to better illuminate the disclosureand does not pose a limitation on the scope of the disclosure unlessotherwise claimed. No language in the specification should be construedas indicating any non-claimed element as essential to the practice ofthe disclosure.

While the foregoing written description enables one of ordinary skill tomake and use what is considered presently to be the best mode thereof,those of ordinary skill will understand and appreciate the existence ofvariations, combinations, and equivalents of the specific embodiment,method, and examples herein. The disclosure should therefore not belimited by the above described embodiment, method, and examples, but byall embodiments and methods within the scope and spirit of thedisclosure.

All documents referenced herein are hereby incorporated by reference.

1. A coating and curing apparatus, comprising: a conveyor system of acombination roll coating and curing facility, wherein the combinationroll coating and curing facility comprises at least one roll coatingfacility followed by at least one curing facility, the at least one rollcoating facility comprising a doctor roller and an application roller,and wherein the conveyor system is adapted to transport a substantiallyflat substrate first through the roll coating facility and afterwardsthrough the curing facility; a source of a sol-gel coating for use inthe combination roll coating and curing facility, the source comprisingspace for a reservoir of the sol-gel coating material between the doctorroller and the application roller of the roll coating facility, thereservoir in fluid communication with the doctor roller and theapplication roller; a processor that controls a process parameter of theat least one roll coating facility; and an air knife of the at least onecuring facility, wherein the air knife is adapted to direct a heated airstream to a portion of the flat substrate as it is transported throughthe at least one curing facility, wherein the at least one roll coatingfacility is adapted to coat the substantially flat substrate with acontinuous film of sol gel coating material and wherein the air knife isadapted to cure the continuous sol gel coating material while aninterior of the substantially flat substrate remains at a temperaturesubstantially lower than a temperature of air from the air knife.
 2. Theapparatus of claim 1, wherein the conveyor system is configured forcoating a solar module.
 3. The apparatus of claim 1 further comprisingan electrical element disposed within the heated air stream to heat theair flowing through the air knife.
 4. The apparatus of claim 1, whereinthe air is heated to a temperature between about 300° C. and 1000° C. 5.The apparatus of claim 1 further comprising a fan in the heated airstream that directs air through an electrical element heater to theair-knife.
 6. The apparatus of claim 1, further comprising an electroniccontroller that controls a temperature of the heated air stream based onreadings from at least one temperature sensor located in the heated airstream.
 7. The apparatus of claim 1, further comprising an exhaust toremove heated air from the apparatus.
 8. The apparatus of claim 1,further comprising a flat plate attached to the leading edge of theair-knife, wherein the flat plate is adapted to form a pre-heat chamberwith the top surface of the substantially flat substrate.
 9. Theapparatus of claim 1, further comprising an infra-red emitter disposedalong the conveyor system as part of the curing facility and prior tothe air knife, wherein the infra-red emitter is adapted to heat thesubstantially flat substrate to a temperature of between 25° C. to 200°C.
 10. The apparatus of claim 1, further comprising an infra-red emitterdisposed along the conveyor system subsequent to the air knife, whereinthe infra-red emitter is adapted to maintain the flat substrate at atemperature of between 120° C. to 400° C.
 11. The apparatus of claim 1,wherein the process parameters comprise at least one of: i. a doctorroller spacing; ii. pressure to an application roller, the applicationroller spacing or pressure taken with respect to the substantially flatsubstrate; a speed at which the substantially flat substrate is conveyedby the conveyor system; and in the case of reverse roll-coating, adifference in speed between the substantially flat substrate and theapplication surface of the application roller.
 12. The apparatus ofclaim 1, wherein the processor further controls a process parameter ofthe curing facility.
 13. The apparatus of claim 1, wherein a pluralityof roll coating facilities and curing facilities are arrangedsequentially.
 14. The apparatus of claim 1, wherein the air-temperatureexiting the air knife is between 500° C. to 750° C.
 15. The apparatus ofclaim 1, wherein the conveyor system through the processor, isconfigured to convey the substantially flat substrate at a speed between0.25 cm/s and 3.5 cm/s.
 16. The apparatus of claim 1, wherein the curingfacility is configured to maintain a surface of the substantially flatsubstrate between 150° C. to 600° C. while an inner temperature does notexceed 100° C.-120° C.
 17. A method of coating and curing, comprising:conveying a substantially flat substrate to be coated with a conveyorsystem through a combination roll coating and curing facility, whereinthe combination roll coating and curing facility comprises at least oneroll coating facility with a doctor roller, an application roller and asource of a sol gel coating in fluid communication with the doctorroller and the application roller and at least one curing facility tocure the sol-gel coating after the sol-gel coating is applied to thesubstantially flat substrate by the at least one roll coating facility;roll coating the substantially flat substrate with a continuous film ofthe sol gel coating material with the at least one roll coatingfacility; and curing the sol gel coating material on the substantiallyflat substrate with an air knife of the at least one curing facility,wherein the air knife is adapted to direct heated air to a portion ofthe substantially flat substrate as it is transported through the curingfacility by the conveyor system, wherein the air knife is adapted tocure the sol gel coating material while an interior of the substantiallyflat substrate remains at a temperature substantially lower than atemperature of air from the air knife.
 18. A sol-gel coatedsubstantially flat substrate formed by the method of claim 17, wherein aportion of the sol-gel coating material is cured while a differentportion of the sol-gel coating material remains uncured.
 19. A method oftuning the performance of a sol gel coating, comprising: determining adesired cure temperature profile to achieve a specific performancemetric for a sol gel coating using at least one physical analysismethod; selecting settings for an air knife curing system's operatingparameters to achieve the desired temperature profiles for the sol gelcoating on a substantially flat substrate; and curing the sol-gelcoating on the substantially flat substrate with the air knife curingsystem, wherein the air knife is adapted to cure the sol gel coatingwhile an interior of the substantially flat substrate remains at atemperature substantially lower than a temperature of air from the airknife.
 20. The method of claim 19, wherein the at least one physicalanalysis method comprises at least one of thermogravimetric analysis,Fourier transform infrared spectroscopy, ellipsometry, nanoindentation,abrasion testing, spectrophotometry, and a water contact anglemeasurement.
 21. The method of claim 19, wherein the air knife curingsystem operating parameters comprise at least one of substrate speed,air knife air-flow volume, air knife output air temperature, air knifeopening distance to substrate surface, a temperature set-point for apre-heating zone and a temperature set point for a post heating zone.22. The method of claim 19, wherein the performance metric for thesol-gel coating comprises at least one of hardness, abrasion resistance,surface energy, refractive index, optical transmission, thickness andporosity.
 23. The method of claim 19, further comprising a step ofcoating the substantially flat substrate with the sol gel coating usinga roll-coating system before the step of curing.
 24. A sol-gel coatedsubstantially flat substrate formed by the method of claim 19, whereinthe specific performance metric comprises a hardness of the sol-gelcoating within a range of 0.2 GPa to 10 GPa.
 25. A sol-gel coatedsubstantially flat substrate formed by the method of claim 19, whereinthe specific performance metric comprising a test in which no more than1% of absolute optical transmission is lost after at least 500 strokesof an abrasion test performed in accordance with specification EN1096-2.26. A sol-gel coated substantially flat substrate formed by the methodof claim 19, wherein the specific performance metric comprises a watercontact angle test in which the water contact angle is within 60° to120°.
 27. A sol-gel coated substantially flat substrate formed by themethod of claim 19, wherein the specific performance metric comprises awater contact angle test in which the water contact angle ranges from 5°to 30°.
 28. A sol-gel coated substantially flat substrate formed by themethod of claim 19, wherein the specific performance metric comprises arefractive index of the cured, coated sol gel from 1.25 to 1.45.
 29. Asol-gel coated substantially flat substrate formed by the method ofclaim 19, wherein the specific performance metric comprises a thicknessof the cured sol gel coating from 50 nm to 150 nm.
 30. A sol-gel coatedsubstantially flat substrate formed by the method of claim 19, wherein asacrificial component of the sol-gel coating is volatilized to form adesired porosity.